Process for treating fabrics and fabrics obtained therefrom

ABSTRACT

The process for producing unusual effects in a three-component fabric having a facing component having upstanding fibers, a backing component and a water-insoluble interlayer component securing the facing component to the backing wherein the entire facing component, the entire backing component, or both the entire facing and backing components are subjected to chemically promoted shrinkage. Laminates obtained are described.

United States Patent Gregorian et al.

[ Apr. 29, 1975 PROCESS FOR TREATING FABRICS AND FABRICS OBTAINEDTI-IEREFROM Inventors: Razmic S. Gregorian, Aiken, SC;

I-Ians R. Hoernle, Augusta, Ga.

Assignee: United Merchants and Manufacturers, Inc., New York, NY.

Filed: Dec. 11, 1973 Appl. No.: 423,683

Related U.S. Application Data Division of Ser. No. 209,456, Dec. 17,1971, Pat. No. 3,797,996.

U.S. Cl 8/ll4.5; 8/130.1 Int. Cl D06m 15/20 Field of Search 8/114.5,130.1; 156/84,

References Cited UNITED STATES PATENTS 3/1938 Castles 28/1 2,239,9144/1941 Heberlein 8/114.5 X 2,245,289 6/1941 156/84 X 2,390,386 12/1945Radford 8/l30.1 X 3,079,212 2/1963 Fountain et al 8/114.5 3,238,5953/1966 Schwartz et al.. 156/85 X 3,553,066 1/1971 Cavalier et al....156/84 X 3,622,434 11/1971 Newman 156/85 X 3,692,603 9/1972 Rhodes156/85 Primary ExaminerLeland A. Sebastian Attorney, Agent, or Firm-JohnP. McGann, Esq.; Jules E. Goldberg, Esq.

[57] ABSTRACT 8 Claims, No Drawings PROCESS FOR TREATING FABRICS ANDFABRICS OBTAINED THEREFROM CROSS REFERENCE TO RELATED APPLICATIONS Thisapplication is a division of copending application Ser. No. 209,456,filed on Dec. 17, 1971, now US. Pat. No. 3,797,996.

BACKGROUND OF THE INVENTION 1. Field of the Invention This inventionpertains to the field of finishing treatments for fabrics. Moreparticularly, this invention concerns methods for chemically affectingunusual texturi zation and color effects in three-component fabricshaving a. facing component of upstanding fibers, a backing component anda water-insoluble interlayer securing the facing component to thebacking component.

2. Description of the Prior Art The use of chemical shrinking agents toshrink woven and non-woven fabrics is known. Techniques for applyingsuch shrinking agents as well as the preferred shrinking agents forvarious types of textiles fibers are also known. (See for example Bull.Inst. Textile France No. l02, pages 871-885 (1962).

A type of fabric to which such chemical shrinking techniques have notnormally been applied are threecomponent fabrics. Such fabrics aregenerally composed ofa facing component as hereinabove described, a baseor backing component which provides the fabric with its structuralstrength and a water-insoluble interlayer, usually an adhesivesubstance, which interlayer secures the facing component to the backingcomponent.

Because ofthe three-component nature of such laminates, thetexturization processes used heretofore have been limited generally tophysical methods, such as, for example, mechanically cutting,compressing or compacting areas of the upstanding fibers of the facingcomponent. These methods, however, tend to require complicated equipmentresulting in relatively high production costs.

SUMMARY OF THE INVENTION We have discovered a new three-component fabriccomprising a facing component of upstanding fibers, a backing component;and a water-insoluble, substantially continuous interlayer disposedbetween the facing component and the backing component and securing thefacing component to the backing component wherein either the backingcomponent or portions thereof, the entire facing component, or both theentire facing and backing components are shrunken.

Additionally, we have discovered that by using a napped backingcomponent, highly unusual and desirable effects may be achieved by usingboth chemical and non-chemical shrinking techniques.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The fabrics which are subjectedto the process of the present invention comprise essentiallythreecomponent laminates having a top or facing component, a backingcomponent and an interlayer component anchoring the facing component tothe backing component.

The facing component may be any type of upstanding or raised fibers,including single fibers as well as fibers in the form of loops and thelike. Suitable materials for use as the facing component include rayon,cotton, nylon, polyesters, wool, mohair, silk, acrylics, modacrylics,and the like. The type of textile material used is not critical so longas it can be shrunken.

The most well known form for the fibers in the facing component is thatof a flock which comprise short fibrous or filamentry material generallyless than a onefourth of an inch in length. This flock is usuallydeposited upon an adhesive coated base. However, as noted hereinabove,the fabrics of the present invention include those having facingcomponents which would not necessarily be within the description offlock generally known to the skilled art worker. For example, the raisedfibers may be looped, or longer than a conventional flock material.Thus, types of fabrics which are suitably within the framework of thepresent invention are velvet fabrics, flocked fabrics, wallcoverings,etc., carpeting or other types of three-component floor covering, etc.

The production of flocked fabrics are well known to the art (see forexample US. Pat. No. 3,079,212 incorporated herein by reference).

The backing component is a flexible backing and may be made ofmaterials, e.g., polyvinyl and urethane films; woven and non-wovenfabrics, and fabrics composed of cellulose-based fibers, e.g., rayon orcotton, and synthetic and natural fibers. Particularly preferred blendsare those of cellulose-based fibers, wool, mohair, silk, acrylics,modacrylics, and the like.

Desirably the backing component itself has upstanding fibers such as inthe form of a nap or pulled loops. Such upstanding fibers are veryshort, generally having a length in the range from about /2 mm to 20 mmand most preferably about 1 mm to 2 mm, although fibers as long as 2-3cm or longer may be used.

The use of a backing component having such raised or upstanding fibersproduces particularly desirable effects when the interlayer is adjacentto it, i.e., the interlayer contacts the napped side of the backingcomponent.

Suitable materials for the interlayer component include adhesivesnormally used to bind fibrous material to backings. Such adhesives aregenerally classified as water base and solvent base adhesives.

Water base adhesives consist of a binder, generally an emulsion polymer,and a viscosity builder. They may also contain plasticizers,thermosetting resins, curing catalysts, stabilizers and other additiveswell known in the art.

The emulsion polymers generally used include acrylic, vinyl-acrylic,vinyl, urethane and styrenebutadiene latexes. In order that theupstanding fibers be held in the desired position until the adhesive isfully cured, it is generally necessary to raise the viscosity of thelatex to about 30 to 100 thousand centipoises. The viscosity is dictatedby the nature of the backing and the method of contacting the upstandingfibers with the adhesive layer. For example, where the backing is aloose weave fabric and the beater bar method is employed, a viscosity offrom to thousand centipoises or higher will be necessary to preventundue penetration of adhesive into the backing which would result in aboardy hand and would leave insufficient adhesive on the surface tosecurely bind the fibers. On the other hand where a relativelyimpervious backing is used, a much lower viscosity, e.g., about 20 to 30thousand centipoises is sufficient.

Suitable thickeners include water soluble polymers such as carboxymethylcellulose, hydroxyethyl cellulose, polyoxyethylenes, and natural gums aswell as alkali swellable polymers such as highly carboxylated acrylicemulsion polymers.

Plasticizers may be added to alter the hand of the finished goods or toimprove the flow and leveling characteristics of the adhesives. Wherethe primary goal is the latter, fugitive plasticizers such as thephthalate esters may be employed. lf the intent is to alter the hand ofthe finished goods, then more permanent plasticizers such as lowmolecular weight polyesters may be used.

Thermosetting resins such as methylol-melamines, urea formaldehydecondensates or phenolformaldehyde condensates may be incorporated toimprove durability or abrasion resistance of the finished goods.

Catalysts such as oxalic acid or diammonium phosphate can be used toincrease the rate of cure of the adhesive.

More specialized additives include ultra-violet absorbers where thebacking, such as urethane foam, is subject to photo degradation and dyesor pigments to impart a color to the adhesive layer. When a breathablefilm is desired, adhesives may be chemically or mechanically foamed.

Solvent adhesives include both fully reacted soluble polymers such asacrylic homo and copolymers, polyesters, polyamides, or polyurethanesand two package systems such as polyester polyols with diisocyanates orisocyanate prepolymers and epoxies with polyamines. The polymer orprepolymer is dissolved in a suitable solvent which is preferably lowboiling, and then thickened to the proper viscosity in a manner similarto that used for the water base adhesives. Catalysts, crosslinkingagents, stabilizers, pigments, or dyes may also be incorporated.

The texturized laminate of the present invention may be prepared byfirst applying a shrinking agent to the desired component of thelaminate. The shrinkage agent may be applied in the form of a pastecomposition by printing. Methods for formulating such pastes as well asthe printing thereof are well known in the art. Thus, for example, theprinting may be carried out on conventional color and dye printingmachines, such as, rotary screen, silk screen, rollers, etc.

Alternatively, the shrinkage agent may be applied by spraying, ordipping. Such spraying and clipping techniques are also conventional.

Many types of well known chemical shrinking agents may be used dependingon the nature of the fibers comprising the component to be shrunken andthe other components of the laminate. Thus, it is understood that theshrinking agent should be a material which will not chemically attackeither the interlayer or the component which is not being shrunken.Moreover, in all cases, the residue of the shrinking agent should bereadily removable in a back washing step, such as, for example, a mildlyalkaline back wash which would be used to remove acidic agents from afacing component made of nylon.

Additionally, shrinking agents should be avoided which would readilydiffuse through the adhesive layer or cause a weakening of thesecurement of the facing component to the backing component.

When the component to be shrunken is nylon, the shrinkage agent shouldbe an acidic material having a dissociation constant greater than about2 X 10*. Suitable acidic materials include strong mono and polybasicinorganic acids and organic acids having the formula R-COOH wherein R ishydrogen, lower alkyl having 1- to 5 carbon atoms or halogen substitutedlower alkyl. Particularly suitable acids include acrylic acid, formicacid, monochloroacetic acid, dichloroacetic acid, alphachloropropionicacid, bromoacetic acid, tricluoroacetic acid, o-chlorobenzoic acid, 3,5,-dinitrobenzoic acid, sulfonic acids, such as, p-toluenesulfonic acid,benzenesulfonic acid, and phenols, sich as, m-cresol, andp-chlorophenol.

The mineral acids, such as, hydrochloric and sulfuric acids are alsosuitable providing they are utilized in a sufficiently diluted form tominimize fiber degradation.

When the component to be shrunken is a polyacrylic material, theshrinking agent may be an acid such as defined hereinabove as beingsuitable for nylon; a salt formed from cations selected from the groupconsisting of Zn, Ag, Ni, Co, Mn, and an anion selected from the groupconsisting of SCN, l Br, and Cl; disubstituted amides having the formulawherein R is hydrogen or lower alkyl having from 1 to 5 carbon atoms, orlower alkyl carbonates, the alkyl portions of which contain 1 to 5carbon atoms.

Particularly suitable shrinking agents for polyacrylics includealpha-chloroacetic acid, trifluoroacetic acid, hydrochloric acid, nitricacid, sulfuric acid, zinc iodide, silver iodide, ethylene carbonate,propylene carbonate and dimethyl acetamide.

When the component to be shrunken is a cellulosic derived material, thethe shrinking agent should be a basic material. Suitable shrinkingagents for cellulo'sics include inorganic bases such as sodiumhydroxide, potassium hydroxide, barium hydroxide, ammonia, strongorganic bases having a dissociation constant greater than about 2 X 10*,such as benzyltrimethylammonium hydroxide and tetraethylammoniumhydroxide, and organic amines such as, ethylamine, triethyl amine,diisopropryl amine, dibutyl amine, ethylene diamine, triethylenetetramine, and the like.

When the shrinking agent is applied in the form of a paste theconcentration and viscosity of the shrinking agent will vary dependingon the amount of shrinkage and effects desired. Although generally theshrinking agent is in an aqueous solution or mixture, it is possibledepending on the laminate used and the shrinking agent to use othersolvents.

The viscosity of the mixture or paste is usually varied by adding athickening agent in a manner well known in the art. The preparation ofsuch pastes are well known to the art and, of course, the rheology ofthe paste will depend on the thickening agent used.

After the application of the shrinking agent to the component, thelaminate is dried. The conditions of drying will depend not only on thereactivity and the concentration of the shrinking agent, but also on thenature of the heating mechanism and the type laminate being shrunk. Thusfor example, when conventional laboratory ovens are used to affectshrinkage of cellulosics, the sodium hydroxide shrinking agentconcentration is preferably in the range from about 30 percent to 50percent and the heating is preferably carried out at a temperature inthe range from about 80 to 125C. When high pressure steam-heated, candryers of the conventional type normally found in textile mills areused, the preferred concentration range for sodium hydroxide whentreating a cellulosic material is from about to 25 percent.

When a volatile shrinking agent is used, it is generally preferable toheat the material with the shrinking agent thereon in an autoclave. Ofcourse, if a more reactive shrinking agent is used, the drying may becarried out at a lower temperature. Thus, for example, with veryreactive shrinking agents, it is possible to dry at room temperature.

Consequently, the drying operation can be carried out in a temperaturerange from about ambient to a temperature limited only by thedegradation temperature of the components of the laminate. Usually, thepreferable operating temperature would be in the range from about 80to160C.

After the drying step, the fabric is washed to remove any remaining orresidual shrinking agent. The components and pH of the backwash, will,of course, depend on the nature of the shrinking agent. Usually it ismost desirable for economic reasons that the back washing solution beaqueous.

When the shrinking agent is an acid having a dissociation constantgreater than about 2 X 10*, an aqueous wash solution containing arelatively weak base such as, for example, sodium carbonate, trisodiumphosphate, or ammonia can be used. When the shrinking agent is a weakacid such as phenol, a more alkaline washing solution may be required.

If the shrinking agent is an alkaline material having a dissociationconstant greater than about 2 X 10*, an aqueous solution containing anyinorganic acid with a dissociation constant greater than about 1 X 10'can be used. It is understood, of course, that the washing solution mustnot contain any materials which will either degrade the materialscomprising the laminate or attack the adhesive interlayer.

It is also possible, when the shrinking agent is an organic solvent, toremove any residual shrinking agent by steaming or volatilization as bypassing the laminate through ovens or over hot cans.

As noted hereinabove, the backing component may possess raised fibers inthe form of a nap or loops. Usually, such raised fibers are mostconveniently obtained by napping the backing fabric.

We have further discovered that when a fabric having a backingpossessing raised fibers or nap as described hereinabove is used, andboth the facing and the backing components are shrunken by eitherchemical or physical means, a highly unusual rippled effect is producedin the facing component. As noted, the shrinkage treatment in this casemay be carried out either by the application of chemical shrinkingagents or by physical shrinking means such as for example, heat. Typicalof such physical shrinkage treatments is the application of steam, ordyeing in a hot dye bath.

If, however, the backing does not possess such raised fibers, an overalldensification effect is produced in the facing component simulating asuede fabric.

Similarly, other unusual effects may be obtained by using a fabrichaving a backing possessing raised fibers and either shrinking only thebacking component or the facing component.

A particularly desirable effect is obtained when a fabric having abacking component possessing raised fibers is subjected to a shrinkagetreatment wherein the shrinking agent is applied only to the backingcomponent in a pre-selected design pattern. That is to say, the entirebacking component is not subjected to shrinkage, but only portionsthereof are shrunken. Such treatment produces contrasting rippled andunrippled areas on the facing component.

In addition to the difference in sculptured effect obtained on thefacing of the fabric by virtue of the foregoing processes, multi'shadeeffects are also obtained as a result of the variation in densificationof the raised fibers of the facing component.

The following examples illustrate our invention: (In the Examples, theadhesive used was an aqueous based acrylic binder unless otherwisenoted).

EXAMPLE 1 A fabric comprising a woven rayon backing substrate and a 1%mm. rayon flock, with the flock anchored to the backing substrate by anadhesive was completely immersed in a 20 percent solution of sodiumhydroxide for 1 minute at room temperature. Without removing the excessliquid by padding, the fabric then was washed in water (50C), rinsed ina 10 percent acetic acid solution and rinsed in water again. The fabricwaspadded to remove the excess water and was then dried at C.

The modified fabric exhibited a natural skin-like appearance with theflock pointing into various directions thereby creating a random patternon the flocked surface and a multi-tone effect. The multi-tone effectwas enhanced by dyeing the fabric according to methods well known in theart with any type of dye or color desired.

EXAMPLE 2 A cotton fabric flocked with a 2 mm. rayon flock wascompletely immersed in a mixture of liquid ammonia and methylenechloride (50:50) for 1 minute. The excess liquid was removed from thefabric by padding. The fabric was air-dried.

The treated substrate resembled a seal-skin. The pile pointed into onedirection and exhibited a natural sheen.

EXAMPLE 3 A rayon substrate flocked with a /2 mm. rayon flock wascompletely immersed in a 10 percent solution of sodium hydroxide for 1minute at room temperature. Without prior padding, the fabric was washedin warm water (50C.), rinsed in an 8 percent acetic acid solution andrinsed in water again. The fabric was padded to remove excess water andwas then dried at 100C.

A substrate with a natural suede-like character resulted.

EXAMPLE 4 A fabric comprising a woven rayon backing substrate and a 1mm. nylon flock with the flock being anchored to the backing substrateby an adhesive was immersed in a 75 percent acrylic acid/water solutionfor 3 minutes at room temperature. The treated substrate was rinsed withwater until the pH of the rinsing water was approximately 7. Excesswater was removed by padding. The fabric was dried at 90C.

The modified substrate exhibited a refined velvet-like look.

EXAMPLE 5 A fabric comprising a non-woven acrylic backing material and amm. rayon flock with the flock being anchored to the backing material byan adhesive was knife-coated on the flocked side with a paste composedof 20 percent sodium hydroxide, 5 percent carboxymethyl starch, and 75percent water. The coated fabric was dried at 100C. for 4 minutes. Thefabric was washed in warm water (50C.), rinsed in a percent acetic acidsolution, and rinsed again in water. Excess water was removed bypadding. The fabric was dried at 100C.

The treatment produced a suede-like substrate.

EXAMPLE 6 A heavily napped non-woven rayon substrate comprising nappedfibers of approximately 1% cm. in length was coated with an aqueousbased acrylic flock binder on the napped side by means of a coatingknife. The coated substrate was flocked with a rayon flock, 2 mm. inlength. The fabric was cured for minutes at 145C.

The flocked fabric then was coated on the back side with a pastecomposed of 40 percent sodium hydroxide, 3 percent carboxymethylatedstarch and 57 percent water. The paste was allowed to penetrate into thebacking substrate for 5 minutes. The fabric then was dried at 140C. for10 minutes. The fabric was washed in water of approximately 65C., rinsedin a 10 percent acetic acid solution, rinsed again in water followed bysqueezing and drying of the fabric. The fabric was dyed with a sulfurdye (C.l. No. 53571) according to conventional methods.

The fabric exhibited a two-tone effect and a heavily rippled andcrimpled flock surface with an appearance similar to Persian lamb woolor an astrochan fur.

EXAMPLE 7 A cotton flannel with a medium degree of napping was coated onthe napped side with an aqueous based acrylic flock binder. The coatedfabric was flocked with rayon flock 1 mm in length and was then curedfor 10 minutes at 140C. A checkerboard pattern was printed onto thebacking substrate with a paste composed of percent sodium hydroxide, 3percent carboxymethylated starch and 77 percent water. The printedfabric was dried for 4 minutes at 140C, washed in water of 70C, rinsedin a 10 percent acetic acid solution, rinsed again in water and was thensqueezed and dried. The fabric was dyed with a sulfur dye (l. C. No.-5357l) according to conventional methods.

The resulting fabric exhibited a quilt-like effect, in that the areaswhich did not come in contact with the shrinking agent puckeredproducing an overall threedimensional effect. In addition, the areaswhich were shrunk by the paste exhibited a rippled and two-toned effect.

EXAMPLE 8 A cotton flannel was napped in preselected areas to produce adesign comprising napped and un-napped areas. The fabric was then coatedoverall with an aqueous based acrylic flock binder on the side which wasnapped in preselected areas. The coated fabric was flocked with a rayonflock 1 mm in length and cured for 15 minutes at 140C.

The flocked fabric was coated overall on the backside with a pastecomprising 20 percent sodium hydroxide, 3 percent carboxy-methylatedstarch and 77 percent water. The backcoated fabric was dried for 3minutes at 140C, washed in water having a temperature of 80C, rinsed ina 10 percent acetic acid solution and rinsed again in water. The waterwas removed by squeezing and the fabric was dried and dyed with a sulfurdye (C. I. No. -53571 according to standard procedures.

A flocked fabric resulted with areas exhibiting a three-dimensionalrippled and two-toned effect and with areas exhibiting a smooth, twodimensional flock surface and a one-toned effect.

EXAMPLE 9 A woven and heavily napped polyester substrate was coated withan aqueous based acrylic flock binder on the napped side. The coatedsubstrate was flocked with rayon flock 2 mm. in length. The fabric wascured for 15 minutes at C.

The fabric was exposed to a temperature of C. for 7 minutes. Aftercooling to room temperature, the fabric was dyed at 85C. for 20 minutesin a dye bath containing a dispersed dye (Disperse Red 131) and a directdye (C. 1. No. 22120). The fabric was washed in hot water (70C),squeezed, and dried.

The fabric exhibited a two-tone effect and a rippled flock surfaceresembling Persian lambs wool.

Variations can, of course, be made without departing from the spirit andscope of the invention.

Having thus described our invention what we desire to secure and claimby Letters Patent is:

1. A process for making a decorative flocked fabric comprising:

a. coating a substrate with a flock adhesive binder wherein saidsubstrate is a napped fabric composed of textile materials selected fromthe group consisting of nylon, cellulosic materials and polyacrylicmaterials, wherein the binder is applied to the napped side;

b. applying a flock selected from the group consisting of nylon,cellulosic materials, and polyacrylic materials to the coated substrateand permanently securing the flock to the substrate by curing thebinder;

c. applying a chemical shrinkage agent directly onto the flock;

d. drying the fabric; and

e. washing the fabric.

2. The process of claim 1 wherein the chemical shrinkage agent isapplied to selected portions of the flock.

3. The process of claim 1 wherein the flock is nylon and the shrinkingagent is an acid having a dissociation constant greater than about 2 X10 and is selected.

from the group consisting of strong mono and polybasic inorganic acids;organic acids having the formula R-' COOH wherein R is hydrogen, loweralkyl having 1 to 5 carbon atoms, halogen substituted lower alkyl having1 to 5 carbon atoms or a nucleus of the phenyl series; sulfonic acids;and phenols.

4. The process of claim 1 wherein the flock is a cellulosic material andthe shrinking agent is a base selected from the group consisting ofalkali hydroxides, alkaline earth hydroxides, ammonia, and organic baseshaving a dissociation constant greater than about 2 X 5. The process ofclaim 1 wherein the flock is polyacrylic and the shrinking agent is anacid having a dissocation constant greater than about 2 X 10' and isselected from the group consisting of strong mono and polybasicinorganic acids; organic acids having the formula R-COOl-l wherein R ishydrogen, lower alkyl having 1 to 5 carbon atoms, halogen substitutedlower alkyl having 1 to 5 carbon atoms; or a nucleus of the phenylseries; sulfonic acids, phenols; a salt formed from cations selectedfrom the group consisting of Zn, Ag", Ni, Co, Mn and an anion selectedfrom the group consisting of SCN, l, Br, and Cl; a

disubstituted amide having the formula the process of claim 1.

1. A PROCESS FOR MAKING A DECORATIVE FLOCKED FABRIC COMPRISING: A.COATING A SUBSTRATE WITH A FLOCK ADHESIVE BINDER WHEREIN SAID SUBSTRATEIS A NAPPED FABRIC COMPOSED OF TEXTILE MATERIALS SELECTED FROM THE GROUPCONSISTING OF NYLON, CELLULOSIC MATERIALS AND POLYACRYLIC MATERIALS,WHEREIN THE BINDER IS APPLIED TO THE NAPPED SIDE; B. APPLYING A FLOCKSELECTED FROM THE GROUP CONSISTING OF NYLON, CELLULOSIC MATERIALS, ANDPOLYACRYLIC MATERIALS TO THE COATED SUBSTRATE AND PERMANENTLY SECURINGTHE FLOCK TO THE SUBSTRATE BY CURING THE BINDER; C. APPLYING A CHEMICALSHRINKAGE AGENT DIRECTLY ONTO THE FLOCK; D. DRYING THE FABRIC; AND E.WASHING THE FABRIC.
 2. The process of claim 1 wherein the chemicalshrinkage agent is applied to selected portions of the flock.
 3. Theprocess of claim 1 wherein the flock is nylon and the shrinking agent isan acid having a dissociation constant greater than about 2 X 10 5 andis selected from the group consisting of strong mono and polybasicinorganic acids; organic acids having the formula R-COOH wherein R ishydrogen, lower alkyl having 1 to 5 carbon atoms, halogen substitutedlower alkyl having 1 to 5 carbon atoms or a nucleus of the phenylseries; sulfonic acids; and phenols.
 4. The process of claim 1 whereinthe flock is a cellulosic material and the shrinking agent is a baseselected from the group consisting of alkali hydroxides, alkaline earthhydroxides, ammonia, and organic bases having a dissociation constantgreater than about 2 X 10
 5. 5. The process of claim 1 wherein the flockis polyacrylic and the shrinking agent is an acid having a dissocationconstant greater than about 2 X 10 5 and is selected from the groupconsisting of strong mono and polybasic inOrganic acids; organic acidshaving the formula R-COOH wherein R is hydrogen, lower alkyl having 1 to5 carbon atoms, halogen substituted lower alkyl having 1 to 5 carbonatoms; or a nucleus of the phenyl series; sulfonic acids, phenols; asalt formed from cations selected from the group consisting of Zn , Ag ,Ni , Co , Mn and an anion selected from the group consisting of SCN , I, Br , and Cl ; a disubstituted amide having the formula
 6. The processof claim 1 wherein the substrate is a flexible napped fabric selectedfrom the group consisting of woven fabrics, non-woven fabrics, polyvinylfilms and urethane films.
 7. The process of claim 1 wherein saidsubstrate possesses napped and unnapped areas.
 8. The decorativelymodified fabric obtained from the process of claim 1.